Detection of Bacterial Neutral Ceramidase in Diabetic Foot Ulcers with an Optimized Substrate and Chemoenzymatic Probes

Ceramidases (CDases) are important in controlling skin barrier integrity by regulating ceramide composition and affording downstream signal molecules. While the functions of epidermal CDases are known, roles of neutral CDases secreted by skin-residing microbes are undefined. Here, we developed a one-step fluorogenic substrate, S-B , for specific detection of bacterial CDase activity and inhibitor screening. We identified a non-hydrolyzable substrate mimic, C6 , as the best hit. Based on C6 , we designed a photoaffinity probe, JX-1 , which efficiently detects bacterial CDases. Using JX-1 , we identified endogenous low-abundance PaCDase in a P. aeruginosa monoculture and in a mixed skin bacteria culture. Harnessing both S-B and JX-1 , we found that CDase activity positively correlates with the relative abundance of P. aeruginosa and is negatively associated with wound area reduction in clinical diabetic foot ulcer patient samples. Overall, our study demonstrates that bacterial CDases are important regulators of skin ceramides and potentially play a role in wound healing.     

f-block MOFs: A Pathway to Heterometallic Transuranics

A novel series of heterometallic f-block-frameworks including the first examples of transuranic heterometallic ²³⁸U/²³⁹Pu-metal–organic frameworks (MOFs) and a novel monometallic ²³⁹Pu-analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)-MOF formation and reported the first value of a U-to-Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid-state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An-integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An-containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals.     

Optically Controlled Recovery and Recycling of Homogeneous Organocatalysts Enabled by Photoswitches

We address a critical challenge of recovering and recycling homogeneous organocatalysts by designing photoswitchable catalyst structures that display a reversible solubility change in response to light. Initially insoluble catalysts are UV-switched to a soluble isomeric state, which catalyzes the reaction, then back-isomerizes to the insoluble state upon completion of the reaction to be filtered and recycled. The molecular design principles that allow for the drastic solubility change over 10 times between the isomeric states, 87 % recovery by the light-induced precipitation, and multiple rounds of catalyst recycling are revealed. This proof of concept will open up opportunities to develop highly recyclable homogeneous catalysts that are important for the synthesis of critical compounds in various industries, which is anticipated to significantly reduce environmental impact and costs.     

Proton-Induced Spin State Switching in an FeIII Complex

Reversible proton-induced spin state switching of an Fe^III complex in solution is observed at room temperature. A reversible magnetic response was detected in the complex, [Fe^III(sal₂323)]ClO₄ ( 1 ), using Evans’ method ¹H NMR spectroscopy which indicated cumulative switching from low-spin to high-spin upon addition of one and two equivalents of acid. Infrared spectroscopy suggests a coordination-induced spin state switching (CISSS) effect, whereby protonation displaces the metal-phenoxo donors. The analogous complex, [Fe^III(4-NEt₂-sal₂323)]ClO₄ ( 2 ), with a diethylamino group on the ligand, was used to combine the magnetic change with a colorimetric response. Comparison of the protonation responses of 1 and 2 reveals that the magnetic switching is caused by perturbation of the immediate coordination sphere of the complex. These complexes constitute a new class of analyte sensor which operate by magneto-modulation, and in the case of 2 , also yield a colorimetric response.     

Oscillation of 2nd-order Nonlinear Noncanonical Difference Equations with Deviating Argument

The purpose of this paper is to establish some new criteria for the oscillation of the second-order nonlinear noncanonical difference equations of the form \[ \Delta \left( a\left( n\right) \Delta x\left( n\right) \right) +q(n)x^{\beta }\left( g(n)\right) =0,\text{ \ \ }n\geq n_{0} \] under the assumption \[ \sum_{s=n}^{\infty }\frac{1}{a\left( s\right) }<\infty \text{.} \] Corresponding difference equations of both retarded and advanced type are studied. A particular example of Euler type equation is provided in order to illustrate the significance of our main results.     

Electroanalytical performance of a Bismuth/Antimony composite glassy carbon electrode in detecting lead and cadmium

This work reports on the electroanalytical performance of a glassy carbon electrode (GCE) modified with antimony and bismuth (Sb/Bi-GCE) in detecting heavy metal ions using lead and cadmium as model analytes. The electroanalytical performance of the Sb/Bi-GCE surface was compared to the bismuth modified glassy carbon electrode (Bi-GCE) as well as the antimony modified glassy carbon electrode (Sb-GCE). The Sb/Bi-GCE exhibited excellent figures of merit compared to Bi-GCE and Sb-GCE surfaces. For example, the limit of detection for lead was 0.01 ppb using Sb/Bi-GCE and 0.1 and 1 ppb on Bi-GCE and Sb-GCE, respectively.     

New amidino‐benzimidazolyl thiophenes: Synthesis and photochemical synthesis

New amidino‐benzimidazolyl‐substituted bis‐1,2‐(2‐thienyl)ethenes ( 4, 5 , and 6 ) and benzo[1,2‐ b:4,3‐ b′]dithiophenes ( 8, 9 , and 10 ) were prepared by the condensation of amidino‐substituted o‐phenylene diamines with corresponding dialdehydes ( 3 and 7 ). All prepared amidino‐benzimidazolyl‐substituted compounds are of particular interest, because they can serve as intercalators or groove binders on DNA in anticancer therapy. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:218–222, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10126